CN1123847A - Method for growing diamond by hot wire method - Google Patents
Method for growing diamond by hot wire method Download PDFInfo
- Publication number
- CN1123847A CN1123847A CN 94118524 CN94118524A CN1123847A CN 1123847 A CN1123847 A CN 1123847A CN 94118524 CN94118524 CN 94118524 CN 94118524 A CN94118524 A CN 94118524A CN 1123847 A CN1123847 A CN 1123847A
- Authority
- CN
- China
- Prior art keywords
- diamond film
- hot wire
- tungsten filament
- tungsten
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 41
- 239000010432 diamond Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 37
- 239000010937 tungsten Substances 0.000 claims abstract description 37
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 239000012429 reaction media Substances 0.000 claims abstract 5
- 239000007789 gas Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 3
- 235000016768 molybdenum Nutrition 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003450 growing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention belongs to the field of chemical vapor deposition technology, and is especially hot filament process of vapor depositing large area diamond film. The invention aims to effectively utilize a vacuum chamber, save power consumption and effectively grow a large-area diamond film by gas, thereby providing a method for growing the diamond film by vapor deposition by introducing a reaction medium in an arrangement mode that one or more W tungsten wires are vertically suspended at the top of a reaction chamber, and a substrate to be deposited is vertically suspended around the W tungsten wires relative to the W wires. The method can improve the deposition efficiency by 1-4 times, reduce the power consumption and reaction medium and reduce the reaction cost.
Description
The invention belongs to chemical vapor deposition technology, particularly relate to the method that adopts heated filament method vapor diamond deposition film.
The chemical vapor-phase growing diamond film is that hydrogen, methane (or carbon containing organic gas, liquid) by pyrolytic decomposition, are reached the purpose of growing diamond film by the chemical reaction of complexity on base material.Wherein atomic hydrogen has played conclusive effect therein.The method of at present existing gas-phase grown diamond film is as hot wire process, microwave plasma method, plasma jet, O
2-C
2H
2Flames etc. have the deposition method of using value to concentrate on hot wire process, microwave method and the plasma jet method.Because hot wire process has very big advantage in the handiness that increases heated filament and technology, the simple advantage of equipment on big area depositing diamond film, but that shortcoming is the speed of diamond film is slow, and film purity is solely not high.Microwave plasma is because the restriction of microwave source, difficult on big area very growing diamond film, maximum area φ 100mm, the speed of growth and hot wire process are similar, advantage is the purity height of diamond film.Plasma jet method fast growth can reach n+-n hundred μ m/h, improves (having a lot of people to be devoted to this research at present) but area is difficult, and consumption gas, electricity are all very big, and spray gun can not long time continuous working.
Hot wire process is to utilize high-melting point metal or alloy silk (tungsten, molybdenum, rhenium etc.), makes its temperature more than 2000 ℃, decomposes hydrogen and carbonaceous reactant gases.The effective primitive (CxHy, X, Y=0～3) that decomposes is transported to substrate surface and a series of chemical reaction takes place comes growing diamond film.The reaction that plays one of them key is that atomic hydrogen is carved the corruption of the graphite of growth, only stays stable diamond continued growth.
Hot wire process growing diamond film optimum growth speed is (electronics enhancing hot wire process) about 10 μ m/h at present.Adopt horizontal multifibres depositional area can reach φ 100mm.As document " hot wire process large area deposition diamond film and temperature field " " the investigation of materials journal 〉.Reactant gases adopts hydrogen (H
2), methane (CH
4), (alcohol C
2H
5OH, acetone CH
3COCH
3Deng), and add a spot of oxygen.When further increasing depositional area, have some difficulties the homogeneity of the stability of work and film growth when arranging as big area W silk.Now the horizontal of W silk that adopt more, downside is placed base material (base material apart from about W silk 10mm), when further increasing W silk area, (reacted gas is difficult in time discharging disturbing adamantine further growth owing to the interference of factors such as gas flow, make that the centre portions layer-growth rate is slower), the difficult evenly growth of film.Thereby simple by increasing that the W silk is arranged area and the growth area that improves diamond film has certain difficulty, generally speaking, adopt W silk arrangement area to be slightly larger than the method for depositional area at present basically.
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, in order to effectively utilize the space of vacuum chamber, save reactant gases and electric energy, improve the growth efficiency of diamond film, to grow diamond membrane with large area, thereby provide a kind of tungsten filament that in vacuum chamber, vertically hangs, hang deposition substrate around the tungsten filament relatively, producing uniform temperature around when the heating tungsten filament distributes, and feed carbon containing organic gas or liquid is done reactant gases, obtain the hot wire process of uniform big area Buddha's warrior attendant film through deposition.
The object of the present invention is achieved like this:
From the mechanism that transports of effective primitive, through high temperature W silk surface pyrolysated atomic hydrogen, carbon containing precursor (C
xH
y) wait and need to be transported to substrate surface from the W silk two kinds of transport mechanism are arranged, the one, convection current comprises and forcing and free convection, the 2nd, the thermodiffusion mass transport that causes by concentration, thermograde.And convection current does not all have influence to the speed of growth and the quality of diamond film.In other words, the gas flow direction there is no very big influence to the growth of diamond film, and effectively transporting fully of primitive controlled by temperature and concentration gradient.
The hot wire process growth of diamond membrane with large area is to do heated filament and adopt single product Si molybdenum, tungsten, SiC, AlN, SiO with materials such as tungsten filaments
2, Cu etc. cooks substrate, feeding reactant gases is carbon containing organic gas or liquid and hydrogen or the mixed gas that adds minor amounts of oxygen.Reaction chamber in the vacuum chamber is to make with molybdenum sheet, tungsten sheet or other refractory metal and alloy thereof.It is to get one or more tungsten filament vertically to be suspended on the interior reaction chamber top of vacuum chamber that method provided by the invention is manufactured process, tungsten filament is arranged can be single, also can many form a plane or four sides, five shapes (shown in Fig. 1-4), the relative tungsten filament of the substrate for the treatment of the depositing diamond film vertically is arranged in around the W silk, distance is 5-15mm between substrate and the W silk, when the reaction chamber internal pressure is 20-100Torr, W silk temperature is greater than 2000 ℃, substrate temperature reaches 700-1000 ℃, the concentration that feeds reactant gases is 0.2Vol%-5Vol%, the feeding total gas flow rate is 50-1000sccm, at this moment the sedimentation velocity of diamond film is about 0.5V～10 μ m/ hours, and the time of carrying out the deposition growing diamond film deposition is directly proportional with the film forming thickness of shape.The speed of growth with feed reactive gas species, and it is relevant whether to increase bias voltage etc.
The present invention is described in detail below in conjunction with accompanying drawing 1-4 and embodiment:
Fig. 1 is the vacuum chamber inner structure synoptic diagram of hot wire process growing diamond film;
Fig. 2 is that a kind of tungsten filament of the present invention is arranged the enforcement synoptic diagram;
Fig. 3 is that second kind of tungsten filament of the present invention arranged synoptic diagram;
Fig. 4 is that the third tungsten filament of the present invention is arranged synoptic diagram;
1-reactant gases among Fig. 1-4 feeds road, 2-reaction chamber, 3-vacuum chamber, 4-tungsten filament, 5-substrate
Embodiment 1:
Press tungsten filament and the substrate arrangement mode growing diamond film of Fig. 2, get the single tungsten filament (4) of a 0.2mm * long 50mm and do curl, it is suspended on tungsten sheet reaction chamber (2) top, arranges single product Si sheets (5) of 4 10 * 40mm areas around tungsten filament, every Si pitch of fins tungsten filament is at a distance of 10mm.When the tungsten filament heating reaches 2000 ℃, when reaction chamber (2) internal pressure is 30Torr, feed H simultaneously
2+ CH
4Mixed gas, it is H that its gas feeds flow
2: sccm, CH
4: sccm, depositing time can grow the even diamond film of thick 5 μ m in 5 hours on four blocks of base materials.
Embodiment 2:
Carry out the hot wire process growing diamond film by the tungsten filament of Fig. 3 and the arrangement mode of substrate.Detailed process is as follows: 5 tungsten filaments (4) with 0.5 * 100mm vertically are arranged in a row on the top that is suspended on the reaction chamber of making of molybdenum sheet (2), vertically place the substrate (5) of two molybdenums in the both sides of parallel tungsten filament (4), the area of substrate (5) is long 80 * wide 80mm, when the temperature that reaches 30Torr and tungsten filament when the indoor vacuum tightness of vacuum reaches 2200 ℃, feed H
2+ O
2+ CH
4The reactant gases of forming, gas flow are that 500sccm carries out the diamond film that 10 hours deposition growings go out thick 15～20mm.
Embodiment 3:
Carry out the hot wire process growing diamond film by the tungsten filament of Fig. 4 and the arrangement mode of substrate.Detailed process is as follows: 8 tungsten filaments (4) of getting φ 0.8 * 100mm divide two row's parallel suspend to push up at reaction chamber, place 2 Si substrates (5) in parallel tungsten filament (4) outside, its reaction chamber (2) is made of the Mo alloy slice, when the indoor vacuum tightness of vacuum reaches 30Torr and tungsten filament temperature and reaches 2300 ℃, feed reactant gases H
2+ CH
4, 1000sccm carries out the diamond film that 5 hours deposition growings go out thick 8mm.
Embodiment 4:
On the basis of Fig. 4, can vertically be arranged in square to tungsten filament (4), 4 substrates of parallel placement (5) and also can place a substrate (5) around tungsten filament at the end of tungsten filament (4), all the other growth conditionss come growing diamond film with embodiment 3.
Superiority of the present invention: the depositing diamond membrane efficiency can be improved doubly (face of 1-4 Long-pending) this also is equivalent to, and the speed of growth has improved 1-in the constant situation of depositional area 4 times, and be at gas flow, power consumption increases and obtains in the less situation, this The disposable Meteorological of equipment when not only having reduced industrial production, and so that Production cost reduces, and reaches the requirement of large-scale popularization, simultaneously also can be in littler establishing Reach the requirement of large area deposition diamond film on standby.
Claims (4)
1. do heater strip (4) at the indoor tungsten filament of vacuum or other resistant to elevated temperatures material for one kind, pass to hydrogen and carbonaceous gas or liquid and do reaction medium, go up the method for vapour deposition diamond membrane with large area at the base material (5) of multiple material, it is characterized in that: be arranged in 1-5 face shape with one or more tungsten filament and vertically be suspended on interior reaction chamber (2) top of vacuum chamber, base material (5) is parallel to be placed on W silk (4) on every side, the feeding flow is the reaction medium of 50-1000sccm when vacuum tightness reaches 20-100 holder and tungsten filament (4) temperature and reaches 2000 ℃, and depositing time is 2-n ten hours.
2. the method by the described a kind of hot wire process growing diamond film of claim 1 is characterized in that: described base material (5) is to adopt single product Si, molybdenum, tungsten, Sic, AcN, Si
3N
4, material such as Cu makes.
3. by the method for the described a kind of hot wire process growing diamond film of claim 1, it is characterized in that: described reaction medium is H
2+ CH
4, H
2+ O
2+ CH
4, ethanol, acetone.
4. by the method for the described a kind of hot wire process growing diamond film of claim 1, it is characterized in that: can be used to improve the forming core density and the growth velocity of diamond film by applying the plus or minus bias voltage between heated filament and base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118524 CN1123847A (en) | 1994-11-29 | 1994-11-29 | Method for growing diamond by hot wire method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118524 CN1123847A (en) | 1994-11-29 | 1994-11-29 | Method for growing diamond by hot wire method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1123847A true CN1123847A (en) | 1996-06-05 |
Family
ID=5038880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94118524 Pending CN1123847A (en) | 1994-11-29 | 1994-11-29 | Method for growing diamond by hot wire method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1123847A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067119C (en) * | 1996-03-20 | 2001-06-13 | 中国科学院金属研究所 | Method and apparatus for large area high-speed thermal filament chemical vapor deposition of diamond |
| CN1322178C (en) * | 2001-12-14 | 2007-06-20 | 六号元素有限公司 | Coloured diamond |
| CN102719804A (en) * | 2012-07-02 | 2012-10-10 | 兰州大学 | Growing device of gas inner circulation type hot wire chemical vapor deposition (CVD) diamond films |
| CN102011101B (en) * | 2009-09-04 | 2013-06-05 | 清华大学 | Growing device for diamond film |
| CN105755448A (en) * | 2016-03-08 | 2016-07-13 | 浙江大学 | Nano diamond thin film and preparation method thereof |
| CN108660433A (en) * | 2018-05-13 | 2018-10-16 | 太原师范学院 | A kind of preparation facilities and method of diamond film |
| CN109804110A (en) * | 2016-10-04 | 2019-05-24 | 碳能力有限责任公司 | For laying the device and method of carbon-coating |
| CN110629192A (en) * | 2018-06-25 | 2019-12-31 | 廊坊西波尔钻石技术有限公司 | Method and equipment for preparing artificial CVD diamond for jewelry |
-
1994
- 1994-11-29 CN CN 94118524 patent/CN1123847A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067119C (en) * | 1996-03-20 | 2001-06-13 | 中国科学院金属研究所 | Method and apparatus for large area high-speed thermal filament chemical vapor deposition of diamond |
| US9115443B2 (en) | 2001-12-14 | 2015-08-25 | Element Six Technologies Limited | Coloured diamond |
| CN1322178C (en) * | 2001-12-14 | 2007-06-20 | 六号元素有限公司 | Coloured diamond |
| US7910083B2 (en) | 2001-12-14 | 2011-03-22 | Element Six Limited | Coloured diamond |
| CN102011101B (en) * | 2009-09-04 | 2013-06-05 | 清华大学 | Growing device for diamond film |
| CN102719804A (en) * | 2012-07-02 | 2012-10-10 | 兰州大学 | Growing device of gas inner circulation type hot wire chemical vapor deposition (CVD) diamond films |
| CN102719804B (en) * | 2012-07-02 | 2014-12-10 | 兰州大学 | Growing device of gas inner circulation type hot wire chemical vapor deposition (CVD) diamond films |
| CN105755448A (en) * | 2016-03-08 | 2016-07-13 | 浙江大学 | Nano diamond thin film and preparation method thereof |
| CN109804110A (en) * | 2016-10-04 | 2019-05-24 | 碳能力有限责任公司 | For laying the device and method of carbon-coating |
| CN109804110B (en) * | 2016-10-04 | 2021-03-30 | 碳能力有限责任公司 | Apparatus and method for applying a carbon layer |
| US11746415B2 (en) | 2016-10-04 | 2023-09-05 | Carboncompetence Gmbh | Method for applying a carbon layer to a substrate comprising introducing a process gas into a deposition chamber via a gas inlet and gas activation element |
| CN108660433A (en) * | 2018-05-13 | 2018-10-16 | 太原师范学院 | A kind of preparation facilities and method of diamond film |
| CN108660433B (en) * | 2018-05-13 | 2023-10-10 | 太原师范学院 | Device and method for preparing diamond film |
| CN110629192A (en) * | 2018-06-25 | 2019-12-31 | 廊坊西波尔钻石技术有限公司 | Method and equipment for preparing artificial CVD diamond for jewelry |
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